Method for reducing organic substances



' "Patented 20, 193

PATENT OFFICE METHOD Fon REDUCING ORGANIC SUBSTANCES Richard Bayer, Bochum-Gerthe, Germany, as-

signor to Friedrich Uhd Application February 27, 1930,

N Drawing.

e, Dortmund, Germany Serial No. 431,986. In Germany March 6, 1929 GClaims. (Cl. 260-168) My invention relates to a method of reducing organic substances and more particularly phenols. It has particular reference to means whereby compounds of the phenol series including phenol proper as well as higher homologues thereof can easily be hydrogenated in the nucleus as well as" at the hydroxyl group. This method is in some way connected with the method of converting carbonaceous materials into liquidrioroducts, which is disclosed in my copending application -ior patent of the United States, Serial No.

394,393, which has matured into Patent 1,936,819, Nov. 28, 1933, and reference will be had to this process hereinafter. The present application is a continuation in part of Serial Number 394,393, now Patent 1,936,819, Nov. 28, 1933.

In the practice of the methods hitherto known for hydrogenating organic compounds under pressure and during decomposition,'such as the well known process disclosed by Bergius, which comprises treating carbon or its products of dis tillation with hydrogen supplied under pressure,

the phenols are not decomposed. On the other hand if these compounds are subjected to catalytic hydrogenation with metal. catalysts, such as nickel or nickel oxide, either at ordinary pressure according to Sabatier, or under higher pressure according to Ipatiew, compounds hydrogenated in the nucleus but still containing oxygen are obtained, which belong to the cyclohexanol yp I have now ascertained the surprising fact that pure phenol as well as its higher homologues resulting from the fractional distillation of tar; that is, phenolic bodies in general, canbe readily hydrogenated in the-nucleus as well as at-the hydroxyl group with the formation of" compounds of the cyclohexane type ((CH2)xwhich, in the case of the homologues, are related to the terpene hydrocarbons, if these compounds are treated with hydrogen developed during the decomposition under pressure by the reaction of finely divided metals, and more especially iron and water.

If this method is applied to phenol profier, secondary reactions leading to condensation products will occur. Thesecondensation products have a boiling point above 360 C. and are highly viscous. They can be used with great advantage as lubricants. Besides these condensation products there are formed considerable quantities of gaseous hydrocarbons, mainly methane.

' I have further found that these secondary reactions can be prevented from occurring: if,

other oils, preferably such as are also hydrogenatable or such as are formed in the hydrogenation, for instance, tar oils and the hydrogenation products thereof.

In this manner it is, for instance, possible to completely convert tarry products, such as the tar acids, etc., which were formed when sub- 'ecting carbonaceous material, such as brown coal or brown coal producer tar with afinely divided metal and water to the combined action of heatand high pressure, as disclosed in my copending application aforesaid, into neutral oils insoluble in alkalis. The'quantity. of hydrogenated products obtained in this second operation corresponds to the quantity of oxygen containing compounds.

In practicing my invention I'may, for instance, proceed as follows:

Example 1 Bituminous brown coal in finely ground condition, which may be mixed with an oil of high boiling point, is heated in an autoclave under continuous stirring with 50% by weight spongy iron and 50% water to 400-470". The carbon is recovered almost completely in liquid form, '20-30% ofa fraction boiling below 200 and 15-20% boiling between 200 and 300 being obtained. The products boiling above 200 C. contain about 12% tar acids. This latter fraction is subjected to. another treatment with water and spongy iron at 450-470 C. in the autoclave. The product obtained in this second operation is free from tar acids. On distillation about 12% were recovered as a fraction boiling below 180 C., while the rest had boiling points up to 350 C. The lower boiling fraction had a specific gravity of 0,78, the specific gravity of oil obtained in the first operation having amounted to about 0,9.

Example 2 I there were recovered about 30-40% by weight (of the starting mixture) of hydrocarbons boiling up to 180 C. and having a specific gravity of about 0,8. The refractive index was about 1,45. The fractions boiling above 180 C. contain besides some cresols about 1020% or neutral hydrocarbons boiling up to 360 C.

The products hydrogenated in the nucleus,

which are obtained in the reaction, can be converted into aromatic hydrocarbons by dehydrogenation with catalysts, such as metallic nickel, iron, platinum, palladium orthe like.

Various changes may be made in the details disclosed in the foregoing specification without departing from the invention or sacrificing the advantages thereof.

In the claims aflixed to this specification no selection of any particular modification of the invention is intended to the exclusion of other modifications thereof and the right to subsequently make claim to any modification not covered by these claims is expressly reserved.

I claim:--

1. The process of hydrogenating phenol and its homologues which comprises subjecting a mixture of such a compound with liquid water and with a finely divided metal capable of reacting with the water to form hydrogen at temperatures of the order of 400 C., to high temperatures of at least about 400 C. and to high pressures developed autogenously within a closed reaction chamber.

2. The process of hydrogenating phenol and its homologues which comprises subjecting a mixture of such a compound with liquid water and with finely divided iron to temperatures ranging between about 400 to 470 C. and to pressures developed autogenously within a closed reaction vessel.

3. In the reduction of phenol and its homologues, the process which comprises mixing such a compound with a quantity of liquid water and of spongy iron suflicient to produce enough hydrogen to reduce said body and subjecting this mixture to temperatures of the order of 400 to 470 C. and to pressures developed autogenously.

4. In the production of liquid hydrocarbon products from carbonaceous materials, the process which comprises subjecting such a material to the action of water and spongy iron at temperatures of the order of 400 to 470 C. and to pressures developed autogenously, separating a phenol-containing fraction from the reaction products, subjecting said fraction to a second similar treatment with water and spongy iron, and recovering the liquid hydrocarbon products thereby produced.

5. The process of claim 4 in which the carbonaceous material is mixed with an oil prior to treatment.

6. In the reduction of phenols, the process which comprises mixing a carbonaceous material containing phenols with about to per cent of spongy iron and about 20 to 50 per cent of water, heating the mixture in an enclosed chamber to temperatures of the order of 400 to 470 C. and recovering the liquid products thereby produced.

RICHARD BAYER. 

